1,3-Dihydroxybenzene derivatives and colorants containing said compounds

ABSTRACT

1,3-Dihydroxybenzene derivatives of general formula (I) or (Ia) or physiologically tolerated, water-soluble thereof  
                 
 
     wherein R′1 denotes substituted pyridyl group, a pyrimidyl group, a group of formula (IIa) or (IIIa)  
                 
 
     and the dyeing agents for keratin fibers containing these compounds.

[0001] The invention relates to novel m-dihydroxybenzene derivatives andto agents for dyeing keratin fibers containing these compounds.

[0002] In the area of keratin fiber dyeing, particularly hair dyeing,oxidation dyes have attained substantial importance. In this case, thecoloration is produced by reaction of certain developers with certaincouplers in the presence of an appropriate oxidant. Suitable developersare, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol,p-aminophenol, 1,4-diaminobenzene and4,5-diamino-1-(2-hydroxyethyl)pyrazole, and suitable couplers are, forexample, resorcinol, 2-methylresorcinol, 1-naphthol, 3-aminophenol,m-phenylenediamine, 2-amino-4-(2′-hydroxyethyl)aminoanisole,1,3-diamino-4-(2′-hydroxyethoxy)benzeneand2,4-diamino-5-fluorotoluene.

[0003] The oxidation dyes used for dyeing human hair must meet numerousrequirements in addition to that of being able to produce colorations ofthe desired intensity. For example, these dyes must be harmless from atoxicological and dermatological standpoint, and the hair colorationsobtained must have good light fastness, resistance to permanent waving,acid fastness and rubbing fastness. In any case, however, in the absenceof exposure to light, rubbing and chemicals, such colorations mustremain stable over a period of at least 4 to 6 weeks. Moreover, bycombining appropriate developers and couplers, it must be possible tocreate a wide range of different color shades.

[0004] Attempts have already been made to improve the properties ofm-dihydroxybenzenes by introduction of substituents. Thus, for example,resorcinols substituted in the 4-position are known from EuropeanUnexamined Patent Application EP 0 904 774 and WO Unexamined PatentApplication 99/15148. Moreover, German Unexamined Patent Applications DE30 016 905 and DE 198 59 800 teach the use of substitutedm-dihydroxybenzenes in oxidation hair colorants. With the currentlyknown dyeing agents, however, it is not possible to meet therequirements placed on dyeing agents in all respects. Hence, the needcontinued to exist for novel couplers that would meet the aforesaidrequirements to a particularly high degree.

[0005] We have now found that certain 1,3-dihydroxybenzene derivativesof general formula (I) or (Ia) meet the requirements placed on couplersto a particularly high degree and that with most known developers theygive strong color shades having unusual color intensity, light fastnessand wash fastness.

[0006] The object of the present invention are therefore novel1,3-dihydroxy-4-heteroarylbenzene derivatives of general formula (I) orthe physiologically tolerated, water-soluble salts thereof

[0007] wherein

[0008] X denotes oxygen, sulfur or N—R5;

[0009] R1 and R2 can be equal or different and independently of eachother denote hydrogen, a halogen atom (F, Cl, Br, I), a hydroxyl group,a C₁-C₄-alkoxy group, a C₁-C₄-hydroxyalkoxy group, a C₁-C₆-alkyl group,a C₁-C₄-alkylthioether group, a trifluoromethyl group, an —Si(CH₃)₃group, a C₁-C₄-hydroxyalkyl group or a C₂-C₄-dihydroxyalkyl group;

[0010] R3 and R4 can be equal or different and independently of eachother denote hydrogen, a hydroxyl group, a halogen atom, a cyano group,a C₁-C₄-alkoxy group, a C₁-C₆-alkyl group, a C₁-C₄-alkylthioether group,a mercapto group, a nitro group, an amino group, a C₁-C₄-alkylaminogroup a di(C₁-C₄)alkylamino group, a —C(O)H group, a —C(O)CH₃ group, a—C(O)CF₃ group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl group or aC₂-C₄-dihydroxyalkyl group; and

[0011] R5 denotes hydrogen, a C₁-C₆-alkyl group, a C₂-C₄-hydroxyalkylgroup, a phenyl group or an acetyl group.

[0012] Compounds of formula (I) are, for example, the following:

[0013] 1,3-dihydroxy-4-(thiophen-2-yl)benzene;1,3-dihydroxy-4-(1-methyl-1H-pyrrol-2-yl)benzene;1,3-dihydroxy-4-(3-aminothiophen-2-yl)benzene;1,3-dihydroxy-4-(3-chlorothiophen-2-yl)benzene;1,3-dihydroxy-4-(3-methylthiophen-2-yl)benzene;1,3-dihydroxy-4-(3-nitrothiophen-2-yl)benzene;1,3-dihydroxy-4-(4-aminothiophen-2-yl)benzene;1,3-dihydroxy-4-(4-chlorothiophen-2-yl)benzene;1,3-dihydroxy-4-(4-methylthiophen-2-yl)benzene;1,3-dihydroxy-4-(4-nitrothiophen-2-yl)benzene;1,3-dihydroxy-4-(5-nitrothiophen-2-yl)benzene;1,3-dihydroxy-4-(5-aminothiophen-2-yl)benzene;1,3-dihydroxy-4-(5-chlorothiophen-2-yl)benzene;1,3-dihydroxy-4-(5-methylthiophen-2-yl)benzene;1,3-dihydroxy-4-(5-nitrothiophen-2-yl)benzene; [sic-Translator],1,3,5-trihydroxy-4-(thiophen-2-yl)benzene;1,2,3-trihydroxy-4-(thiophen-2-yl)benzene;1,3,6-trihydroxy-4-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methyl-4-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methyl-4-(thiophen-2-yl)benzene;1,3-dihydroxy-6-methyl-4-(thiophen-2-yl)benzene;1,3-dihydroxy-2-chloro-4-(thiophen-2-yl)benzene;1,3-dihydroxy-5-chloro-4-(thiophen-2-yl)benzene;1,3-dihydroxy-6-chloro-4-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methoxy-4-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methoxy-4-(thiophen-2-yl)benzene and1,3-dihydroxy-6-methoxy-4-(thiophen-2-yl)benzene.

[0014] Preferred compounds of formula (I) are those wherein (i) one ormore of the R1, R2, R3 and R4 groups denote hydrogen and X denotessulfur or oxygen or (ii) R1 and R2 simultaneously denote hydrogen and Xdenotes sulfur.

[0015] Another object of the invention are 1,3-dihydroxybenzenederivatives of formula (Ia) or the physiologically tolerated,water-soluble salts thereof

[0016] wherein

[0017] R′1 denotes a substituted pyridyl group, a pyrimidyl group, agroup of formula

[0018] or a group of formula

[0019] wherein R′2, R′3, R′4, R′5 and R′6 independently of each otherdenote hydrogen, a halogen atom (F, Cl, Br, I), a cyano group, ahydroxyl group, a C₁-C₄-alkoxy group, a C₁-C₄-hydroxyalkoxy group, aC₁-C₆-alkyl group, a C₁-C₄-alkylthioether group, a mercapto group, anitro group, an amino group, a C₁-C₄-alkylamino group, ahydroxy(C₁-C₄)alkylamino group, a di(C₁-C₄)alkylamino group, adi[hydroxy(C₁-C₄)-alkyl]amino group, a [dihydroxy-(C₃-C₄)-alkyl]aminogroup, a [hydroxy-(C₁-C₄)-alkyl]-C₁-C₄-alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl group or aC₂-C₄-dihydroxyalkyl group, or two adjacent R2 to R6 groups form an—O—CH₂—O— bridge;

[0020] X′1 denotes sulfur, nitrogen, oxygen, C—R′9 or N—R′8;

[0021] X′2 denotes sulfur, nitrogen, oxygen, C—R′10 or N—R′8;

[0022] X′3 denotes sulfur, nitrogen, oxygen, C—R′11 or N—R′8;

[0023] R′7, R′9, R′10 and R′11 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a C₁-C₄-alkoxygroup, a C₁-C₆-alkyl group, a C₁-C₄-alkylthioether group, a mercaptogroup, a nitro group, an amino group, a C₁-C₄-alkylamino group, adi(C₁-C₄)alkylamino group, a di(C₁-C₄-hydroxyalkyl)amino group, aC₁-C₄-hydroxyalkylamino group, a trifluoromethyl group, a —C(O)CH₃group, a —C(O)CF₃ group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl groupor a C₃-C₄-dihydroxyalkyl group; and

[0024] R′8 denotes hydrogen, a C₁-C₆-alkyl group, a C₂-C₄-hydroxyalkylgroup, a phenyl group or an acetyl group,

[0025] provided that at least one and at the most two X′1 to X′3 groupsdenote C—R′9, C—R′10 or C—R′11 and at the most one of the X′1 to X′3groups denotes sulfur, oxygen or N—R′8, and R′1 does not stand for aphenyl group or hydroxyphenyl group.

[0026] Compounds of formula (Ia) are, for example:

[0027] 1,3-dihydroxy-(thiophen-2-yl)benzene;1,3-dihydroxy-5-(1-methyl-1H-pyrrol-2-yl)-benzene;1,3-dihydroxy-5-(pyrrol-2-yl)benzene;1,3-dihydroxy-5-(furan-2-yl)benzene;1,3-dihydroxy-5-(3-aminothiophen-2-yl)benzene;1,3-dihydroxy-5-(3-chlorothiophen-2-yl)benzene;1,3-dihydroxy-5-(3-methylthiophen-2-yl)benzene;1,3-dihydroxy-5-(3-nitrothiophen-2-yl)benzene;1,3-dihydroxy-5-(4-aminothiophen-2-yl)benzene;1,3-dihydroxy-5-(4-chlorothiophen-2-yl)benzene;1,3-dihydroxy-5-(4-methylthiophen-2-yl)benzene;1,3-dihydroxy-5-(4-nitrothiophen-2-yl)benzene;1,3-dihydroxy-5-(5-nitrothiophen-2-yl)benzene;1,3-dihydroxy-5-(5-aminothiophen-2-yl)benzene;1,3-dihydroxy-5-(5-chlorothiophen-2-yl)benzene;1,3-dihydroxy-5-(5-methylthiophen-2-yl)benzene;1,3-dihydroxy-5-(5-nitrothiophen-2-yl)benzene; [sic-Translator],1,3,5-trihydroxy-5-(thiophen-2-yl)benzene;1,2,3-trihydroxy-5-(thiophen-2-yl)benzene;1,3,6-trihydroxy-5-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methyl-5-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methyl-5-(thiophen-2-yl)benzene;1,3-dihydroxy-6-methyl-5-(thiophen-2-yl)benzene;1,3-dihydroxy-2-chloro-5-(thiophen-2-yl)benzene;1,3-dihydroxy-5-chloro-5-(thiophen-2-yl)benzene;1,3-dihydroxy-6-chloro-5-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methoxy-5-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methoxy-5-(thiophen-2-yl)benzene;1,3-dihydroxy-6-methoxy-5-(thiophen-2-yl)benzene;1,3-dihydroxy-2-(thiophen-2-yl)benzene;1,3-dihydroxy-2-(1-methyl-1H-pyrrol-2-yl)benzene;1,3-dihydroxy-2-(pyrrol-2-yl)benzene;1,3-dihydroxy-2-(furan-2-yl)benzene;1,3-dihydroxy-2-(3-aminothiophen-2-yl)benzene;1,3-dihydroxy-2-(3-chlorothiophen-2-yl)benzene;1,3-dihydroxy-2-(3-methylthiophen-2-yl)benzene;1,3-dihydroxy-2-(3-nitrothiophen-2-yl)benzene;1,3-dihydroxy-2-(4-aminothiophen-2-yl)benzene;1,3-dihydroxy-2-(4-chlorothiophen-2-yl)benzene;1,3-dihydroxy-2-(4-methylthiophen-2-yl)benzene;1,3-dihydroxy-2-(4-nitrothiophen-2-yl)benzene;1,3-dihydroxy-2-(5-nitrothiophen-2-yl)benzene;1,3-dihydroxy-2-(5-aminothiophen-2-yl)benzene;1,3-dihydroxy-2-(5-chlorothiophen-2-yl)benzene;1,3-dihydroxy-2-(5-methylthiophen-2-yl)benzene;1,3-dihydroxy-2-(5-nitrothiophen-2-yl)benzene; [sic-Translator],1,3,5-trihydroxy-2-(thiophen-2-yl)benzene;1,2,3-trihydroxy-2-(thiophen-2-yl)benzene;1,3,6-trihydroxy-2-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methyl-2-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methyl-2-(thiophen-2-yl)benzene;1,3-dihydroxy-6-methyl-2-(thiophen-2-yl)benzene;1,3-dihydroxy-2-chloro-2-(thiophen-2-ylbenzene;1,3-dihydroxy-5-chloro-2-(thiophen-2-yl)benzene;1,3-dihydroxy-6-chloro-2-(thiophen-2-yl)benzene;1,3-dihydroxy-2-methoxy-2-(thiophen-2-yl)benzene;1,3-dihydroxy-5-methoxy-2-(thiophen-2-yl)benzene;1,3-dihydroxy-6-methoxy-2-(thiophen-2-yl)benzene;1,3-dihydroxy-4-(pyridin-2-yl)benzene;1,3-dihydroxy-4-(pyrimidin-2-yl)benzene;1,3-dihydroxy-4-(5-methylpyridin-2-yl)benzene;5-(2,4-dihydroxy-phenyl)nicotinonitrile;1,3-dihydroxy-4-(5-nitropyridin-2-yl)benzene;1,3-dihydroxy--4-(thiophen-3-yl)benzene; 4′-methylbiphenyl-2,4-diol;4′-fluorobiphenyl-2,4-diol;1,3-dihydroxy-4-(4-methylthiophen-3-yl)benzene;2′,4′-dihydroxybiphenyl-4-carbonitrile;1,3-dihydroxy-4-(2-chlorothiophen-3-yl)benzene;1-(2′,4′-dihydroxybiphenyl-3-yl)ethanone;1,3-dihydroxy-4-benzo[1,3]dioxol-5-ylbenzene; 4′-nitrobiphenyl-2,4-diol;2′-nitrobiphenyl-2,4-diol; 4-(5-nitrothiophen-2-yl)benzene;4′-trifluoromethylbiphenyl-2,4-diol; 2′,4′-dimethylbiphenyl-2,4-diol;3′-methoxybiphenyl-2,4-diol; 4′-chlorobiphenyl-2,4-diol;1,3-dihydroxy-5-(pyridin-2-yl)benzene;1,3-dihydroxy-5-(pyrimidin-2-yl)benzene;1,3-dihydroxy-5-(thiophen-3-yl)benzene; 5-thiophen-2-ylbenzene;1,3-dihydroxy-(5-thiazol-2-yl)benzene; 4′-methylbiphenyl-3,5-diol;1,3-dihydroxy-5-(5-methylpyridin-2-yl)benzene;4′-fluorobiphenyl-3,5-diol;1,3-dihydroxy-5-(4-methylthiophen-3-yl)benzene;3′,5′-dihydroxybiphenyl-4-carbonitrile;1,3-dihydroxy-5-(2-chlorothiophen-3-yl)benzene;1-(3′,5′-dihydroxybiphenyl-3-yl)ethanone; 4′-nitrobiphenyl-3,5-diol;2′-nitrobiphenyl-3,5-diol; 4′-trifluoromethylbiphenyl-3,5-diol;2′,4′-dimethylbiphenyl-3,5-diol; 3′-methoxybiphenyl-3,5-diol;4′-chlorobiphenyl-3,5-diol;1,3-dihydroxy-5-(5-nitropyridin-2-yl)benzene;4′-methylsulfanylbiphenyl-3,5-diol; 2′-chloro-4′-nitrobiphenyl-3,5-diol;4′-methylsulfanylbiphenyl-2,4-diol and1,3-dihydroxy-4-(thiazol-2-yl)benzene,

[0028] as well as the physiologically tolerated salts thereof.

[0029] Preferred compounds of formula (Ia) are those wherein:

[0030] (i) X′2 denotes C—R′10 and X′1 denotes sulfur and X′3 denotesC—R′11, or X′1 denotes C—R′9 and X′3 denotes sulfur or (ii) X′2 denotesC—R′10 and X′1 denotes sulfur and X′3 denotes C—R′11 or X′1 denotesC—R′9 and X′3 denotes sulfur, and at least one of the R′9 to R′11 groupsdenotes hydrogen.

[0031] Particularly preferred are the following compounds of formula (I)and (Ia):

[0032] 1,3-dihydroxy-4-(thiophen-2-yl)benzene;1,3-dihydroxy-4-(5-nitrothiophen-2-yl)benzene;1,3-dihydroxy-4-(3-methylthiophen-2-yl)benzene;1,3-dihydroxy-4-(furan-2-yl)benzene;1,3-dihydroxy-5-(5-chlorothiophen-2-yl)benzene;1,3-dihydroxy-5-(3-methylthiophen-2-yl)benzene;1,3-dihydroxy-4-(thiophen-3-yl)benzene and1,3-dihydroxy-5-(thiophen-3-yl)benzene

[0033] as well as the physiologically tolerated salts thereof.

[0034] The 1,3-dihydroxybenzene derivatives of formula (I) and (Ia) canbe prepared by known methods of synthesis. The synthesis of thecompounds of the invention can be accomplished by palladium(O)-catalyzedcoupling (i) of a substituted benzene of formula (II) with a heteroarylcompound of formula (III) or (ii) of a substituted benzene of formula(IIa) with a compound of formula R′1-Rd followed by elimination of theprotective group:

[0035] wherein

[0036] Rb stands for halogen (F, Cl, Br, I) and Rd denotes B(OH)₂, or Rbstands for B(OH)₂ and Rd for halogen (F, Cl, Br, I);

[0037] Ra denotes a protective group as described, for example, in thechapter on “Protective Groups”, in Organic Synthesis, chapter 3, WileyInterscience, 1991, and X, R1, R2, R3, R4 and R′1 have the same meaningas in formula (I) and (Ia).

[0038] The 1,3-dihydroxybenzene derivatives of formula (I) and (Ia) arehighly water-soluble and give colorations of excellent color intensityand color stability, particularly in terms of light fastness, washfastness and rubbing fastness. They also have excellent storagestability, particularly as constituents of the oxidation colorantsdescribed in the following.

[0039] Another object of the present invention are therefore agents foroxidative dyeing of keratin fibers, for example hair, furs, feathers orwool, particularly human hair, based on a developer-coupler combinationcontaining at least one 1,3-dihydroxybenzene derivative of formula (I)or (Ia), and wherein in formula (Ia) R′1 can, in addition to themeanings given in the foregoing, also denote a phenyl group orhydroxyphenyl group.

[0040] The compounds of formula (I) and (Ia) can be used as the freephenols as well as in the form of their physiologically tolerated saltswith inorganic or organic bases, for example, sodium hydroxide,potassium hydroxide, sodium carbonate or tetrabutylammonium hydroxide.

[0041] The 1,3-dihydroxybenzene derivatives of formula (I) and/or (Ia)are present in the colorants of the invention in a total amount of about0.005 to 20 wt. %, an amount of about 0.01 to 5.0 wt. % and particularly0.1 to 2.5 wt. % being preferred.

[0042] Suitable developers are, for example,

[0043] 1,4-diaminobenzene (p-phenylenediamine);1,4-diamino-2-methylbenzene (p-toluyl-enediamine);1,4-diamino-2,6-dimethylbenzene; 1,4-diamino-3,5-diethylbenzene;1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diaminobenzene; 1,4-diamino-2-(thiophen-2-yl)benzene;1,4-diamino-2-(thiophen-3-yl)benzene;1,4-diamino-2-(pyridin-3-yl)benzene; 2,5-diaminobiphenyl;1,4-diamino-2-methoxymethylbenzene; 1,4-diamino-2-aminomethylbenzene;1,4-diamino-2-hydroxymethylbenzene;1,4-diamino-2-(2-hydroxyethoxy)benzene;2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene; 4-phenylaminoaniline;4-dimethylaminoaniline; 4-diethylaminoaniline; 4-dipropylaminoaniline;4-[ethyl-(2-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]-2-methylaniline;4-[(2-methoxyethyl)amino]aniline; 4-[(3-hydroxypropyl)amino]aniline;4-[(2,3-dihydroxypropyl)amino]aniline;1,4-diamino-2-(1-hydroxyethyl)benzene;1,4-diamino-2-(2-hydroxyethyl)benzene;1,4-diamino-2-(1-methylethyl)benzene;1,3-bis-[(4-aminophenyl)-(2-hydroxyethyl)amino]-2-propanol;1,4-bis-[(4-aminophenyl)amino]butane;1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol;4-amino-3-fluorophenol; 4-methylaminophenol;4-amino-2-(aminomethyl)phenol; 4-amino-2-(hydroxymethyl)phenol;4-amino-2-fluorophenol; 4-amino-2-[(2-hydroxyethyl)amino]methylphenol;4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol;4-amino-2-(2-hydroxyethyl)phenol; 5-aminosalicylic acid;2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine;2,5,6-triamino-4-(1H)-pyrimidone;4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-(1-methylethyl)-1H-pyrazole;4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole;1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 2-aminophenol; 2-amino-6-methylphenol;2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.

[0044] In addition to the compounds of formula (I) and/or (Ia), thecolorant of the invention can also contain other known couplers, forexample

[0045] N-(3-dimethylaminophenyl)urea; 2,6-diaminopyridine;2-amino-4[(2-hydroxyethyl)amino]anisole;2,4-diamino-1-fluoro-5-methylbenzene;2,4-diamino-1-methoxy-5-methylbenzene;2,4-diamino-1-ethoxy-5-methylbenzene;2,4-diamino-1-(2-hydroxyethoxy-5-methylbenzene;2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene;2,3-diamino-6-methoxypyridine;3-amino-6-methoxy-2-(methylamino)pyridine;2,6-diamino-3,5-dimethoxypyridine; 3,5-diamino-2,6-dimethoxypyridine;1,3-diaminobenzene;2,4-diamino-1-(2-hydroxyethoxy)benzene;1,3-diamino-4-(2,3-dihydroxypropoxy)benzene;1,3-diamino-4-(3-hydroxypropoxy)benzene;1,3-diamino-4-(2-methoxyethoxy)benzene;2,4-diamino-1,5-di(2-hydroxyethoxy)benzene;1-(2-aminoethoxy)-2,4-diaminobenzene;2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene; 2,4-diaminophenoxyacetic acid; 3-[di(2-hydroxyethyl)amino]aniline;4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene;5-methyl-2-(1-methylethyl)phenol; 3-[(2-hydroxyethyl)amino]aniline;3-[(2-aminoethyl)amino]aniline; 1,3-di(2,4-diaminophenoxy)propane;di(2,4-diaminophenoxy)methane; 1,3-diamino-2,4-dimethoxybenzene;2,6-bis(2-hydroxyethyl)aminotoluene; 4-hydroxyindole;3-dimethylaminophenol; 3-diethylaminophenol; 5-amino-2-methylphenol;5-amino-4-fluoro-2-methylphenol; 5-amino-4-methoxy-2-methylphenol;5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4-dichlorophenol;5-amino-2,4-dichlorophenol; 3-amino-2-methylphenol;3-amino-2-chloro-6-methylphenol; 3-aminophenol;2-[(3-hydroxyphenyl)amino]acetamide;5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol;5-[(2-hydroxyethyl)amino]-2-methylphenol;3-[(2-hydroxyethyl)amino]phenol; 3-[(2-methoxyethyl)amino]phenol;5-amino-2-ethylphenol; 5-amino-2-methoxyphenol;2-(4-amino-2-hydroxyphenoxy)ethanol;5-[(3-hydroxypropyl)amino]-2-methylphenol;3-[(2,3-dihydroxypropyl)amino]-2-methylphenol;3-[(2-hydroxyethyl)amino]-2-methylphenol; 2-amino-3-hydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 5-amino-4-chloro-2-methylphenol;1-naphthol; 2-methyl-1-naphthol; 1,5-dihydroxynaphthalene;1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene;2,7-dihydroxynaphthalene; 2-methyl-1-naphthol acetate;1,3-dihydroxybenzene; 1-chloro-2,4-dihydroxybenzene;2-chloro-1,3-dihydroxybenzene;1,2-dichloro-3,5-dihydroxy-4-methylbenzene;1,5-dichloro-2,4-dihydroxybenzene; 1,3-dihydroxy-2-methylbenzene;3,4-methylenedioxyphenol; 3,4-methylenedioxyaniline;5-[(2-hydroxyethyl)amino]-1,3-benzodioxole;6-bromo-1-hydroxy-3,4-methylenedioxybenzene; 3,4-diaminobenzoic acid;3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine;6-amino-3,4-dihydro-1,4[2H]benzoxazine; 3-methyl-1-phenyl-5-pyrazolone;5,6-dihydroxyindole; 5,6-dihydroxyindoline; 5-hydroxyindole;6-hydroxyindole; 7-hydroxyindole and 2,3-indolinedione.

[0046] The couplers and developers can be present in the colorant of theinvention either individually or in admixture with one another, thetotal amount of each of the couplers and developers in the colorant ofthe invention being about 0.005 to 20 wt. % preferably about 0.01 to 5wt. % and particularly 0.1 to 2.5 wt. % (based on the total amount ofcolorant).

[0047] The total amount of the developer-coupler combination containedin the colorant described herein is preferably about 0.01 to 20 wt. %,an amount of about 0.02 to 10 wt. % and especially 0.2 to 6 wt. % beingparticularly preferred. In general, the developers and couplers are usedin approximately equimolar amounts. In this respect, it is notdisadvantageous, however, if the developers are present in a certainexcess or deficiency.

[0048] Moreover, the colorants of the invention can also contain otherdye components, for example 6-amino-2-methylphenol and2-amino-5-methylphenol, as well as common direct dyes from the group ofacid or basic dyes, triphenylmethane dyes, aromatic nitro dyes, azo dyesand disperse dyes. The colorants of the invention can contain these dyecomponents in an amount from about 0.1 to 4 wt. %.

[0049] The additional couplers and developers and the other dyecomponents, provided they are bases, can of course also be used in theform of their physiologically tolerated salts with organic or inorganicacids, for example hydrochloric acid or sulfuric acid, or—if theycontain aromatic OH groups—in the form of their salts with bases, forexample Moreover, if the colorants of the invention are to be used forcoloring hair, they can also contain other common cosmetic additives,for example antioxidants such as ascorbic acid, thioglycolic acid orsodium sulfite, as well as perfume oils, complexing agents, wettingagents, emulsifiers, thickeners and hair-care agents.

[0050] The colorant of the invention can be in the form of, for example,a solution, particularly an aqueous or aqueous-alcoholic solution. Aparticularly preferred formulation form, however, is a cream, gel oremulsion. Such a composition consists of a mixture of the dye componentsand the usual additives employed for such compositions.

[0051] Common additives to solutions, creams, emulsions or gels are, forexample, solvents such as water, lower aliphatic alcohols, for exampleethanol, propanol or isopropanol, glycerol or glycols such as1,2-propylene glycol, moreover wetting agents or emulsifiers from theclasses of anionic, cationic, amphoteric or nonionic surface-activesubstances, for example fatty alcohol sulfates, ethoxylated fattyalcohol sulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fattyesters, furthermore thickeners such as the higher fatty alcohols,starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids,also hair-care agents such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The said constituents areused in amounts commonly employed for such purposes, for example thewetting agents and emulsifiers at a concentration of about 0.5 to 30 wt.%, the thickeners in an amount from about 0.1 to 30 wt. % and thehair-care agents at a concentration from about 0.1 to 5 wt. %.

[0052] Depending on the composition, the colorant of the invention canbe weakly acidic, neutral or alkaline. In particular, it has a pH of 6.5to 11.5. Adjustment to a basic pH is preferably done with ammonia, butit can also be done with an organic amine, for example monoethanolamineand triethanolamine, or with an inorganic base such as sodium hydroxideand potassium hydroxide. Suitable for adjustment to an acidic pH areinorganic or organic acids, for example phosphoric acid, acetic acid,citric acid or tartaric acid.

[0053] For oxidative dyeing of hair, the afore-described colorant ismixed with an oxidant just before use, and the resulting mixture isapplied to hair in an amount sufficient for the hair-dyeing treatment,in general about 60 to 200 grams, depending on the hair fullness.

[0054] Suitable oxidants for developing the hair coloration are mainlyhydrogen peroxide or its products of addition to urea, melamine, sodiumborate or sodium carbonate, in the form of a 3-12%, preferably 6%aqueous solution, atmospheric oxygen also being suitable. When a 6%hydrogen peroxide solution is used as oxidant, the weight ratio of haircolorant to oxidant is from 5:1 to 1:2, but preferably 1:1. Largeramounts of oxidant are used primarily at higher dye concentrations inthe hair colorant or when stronger bleaching of the hair is wanted atthe same time. The mixture is allowed to act on the hair at 15 to 50° C.for about 10 to 45 min, preferably 30 min, after which the hair isrinsed with water and dried. Optionally, following this rinsing, thehair is washed with a shampoo and optionally post-rinsed with a weakorganic acid, for example citric acid or tartaric acid. The hair is thendried.

[0055] The colorants of the invention containing a 1,3-dihydroxybenzenederivative of formula (I) and/or (Ia) as coupler give hair colorationsof excellent color stability, particularly in terms of light fastness,wash fastness and rubbing fastness. As far as their dyeing propertiesare concerned, the hair colorants of the invention provide a wide rangeof different color shades from blond to brown, purple, violet and evenblue and black, depending on the kind and composition of the dyecomponents. The color shades are noteworthy for their unusual colorintensity. The very good coloring properties of the hair colorant of thepresent patent application also manifest themselves in that thiscolorant makes it possible to dye gray hair, previously not damagedchemically, without any problems and with good covering power.

[0056] The following examples illustrate the object of the invention ingreater detail without limiting its scope.

EXAMPLES Example 1

[0057] Synthesis of 1,3-dihydroxybenzenes (General Method of Synthesis)

[0058] A. Synthesis of2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran

[0059] To a solution of 9.5 g (40 mmol) of 4-bromo-1,3-dihydroxybenzeneand 5 g (20 mmol) of toluene-4-sulfonic acid pyridine salt in 50 mL ofdichloromethane was added dropwise 9 g (105 mmol) of3,4-dihydro-2H-pyran under argon. The reaction mixture was allowed toagitate 18 hours. The reaction mixture was then poured into 100 mL ofethyl acetate and the organic phase was extracted with dilute sodiumhydroxide and then dried with magnesium sulfate. The solvent wasdistilled off in a rotary evaporator, and the residue was purified onsilica gel with petroleum ether/ethyl acetate (7:1).

[0060] This gave 9.5 g (54% of the theoretical) of2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyran.

[0061] B. Synthesis of2-{2-(4,4,5,5-tetramethyl[1,3,2]dioxoborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy}tetrahydro-2H-pyran

[0062] 210 mL of degassed dioxan was added under argon to a mixture of5.5 g (154 mmol) of2-[2-bromo-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy]tetrahydro-2H-pyranfrom step A, 9 g (355 mmol) of4,4,5,5,4′,4′,5′,5′-octamethyl[2,2′]bi{[1,3,2]dioxaborinanyl}, 1,5 g(2.2 mmol) of dichloro-[1,1′-bis(diphenylphosphino)ferrocene]palladium[PdCl₂(dppf)] and 6.2 g (63.2 mmol) of potassium acetate. The mixturewas allowed to agitate at 80° C. for 24 hours and was then poured intowater and extracted with ethyl acetate. The organic phase was washedwith a saturated aqueous solution of sodium chloride, dried over sodiumsulfate and then filtered and evaporated. The resulting crude productwas purified on deactivated silica gel using a gradient of hexane (100%)and hexane/ethyl acetate (9:1 to 3:2).

[0063] This gave 4.70 g (77% of the theoretical) of2-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxoborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy}tetrahydro-2H-pyran.

[0064] C. Synthesis of 1,3-dihydroxybenzenes of Formula (I)

[0065] 0.09 g (0.2 mmol) of2-{2-(4,4,5,5-tetramethyl[1,3,2]dioxoborolan-2-yl)-5-(tetrahydro-2H-pyran-2-yloxy)phenoxy}tetrahydro-2H-pyranfrom step B and 0.04 mmol of the appropriate bromo derivative weredissolved in 10 mL of 1,2-dimethoxyethane under argon. Then, 0.01 g(0.005 mmol) of tetrakis(triphenylphosphine)palladium and 0.26 mL of 2Npotassium carbonate solution were added, and the reaction mixture washeated to 80° C. At the end of the reaction, the reaction mixture waspoured into 10 mL of ethyl acetate, and the organic phase was extractedwith dilute sodium hydroxide solution and then dried with magnesiumsulfate. The solvent was distilled off in a rotary evaporator, and theresidue was purified on silica gel with petroleum ether/ethyl acetate(9:1).

[0066] a. 1,3-Dihydroxy-4-(thiophenyl-2-yl)benzene [sic-Translator]

[0067] Bromo derivative used: 2-bromothiophene

[0068] Mass spectrum: MH⁺ 192 (100)

[0069] b. 1,3-Dihydroxy-4-(5-nitrothiophen-2-yl)benzene

[0070] Bromo derivative used: 2-bromo-5-nitrothiophene

[0071] Mass spectrum: MH⁺ 237 (100)

[0072] c. 1,3-Dihydroxy-4-(3-methylthiophen-2-yl)benzene

[0073] Bromo derivative used: 2-bromo-3-methylthiophene

[0074] Mass spectrum: MH⁺ 206 (100)

[0075] d. 1,3-Dihydroxy-4-(pyridin-2-yl)benzene hydrochloride

[0076] Bromo derivative used: 2-bromopyridine

[0077] Mass spectrum: MH⁺ 188 (100)

[0078] e. 1,3-Dihydroxy-4-(pyrimidin-2-yl)benzene hydrochloride

[0079] Bromo derivative used: 2-bromopyrimidine

[0080] Mass spectrum: MH⁺ 189 (100)

[0081] f. 1,3-Dihydroxy-4-(5-methylpyridin-2-yl)benzene hydrochloride

[0082] Bromo derivative used: 2-bromo-5-methylpyridine

[0083] Mass spectrum: MH⁺ 188 (100)

[0084] g. 5-(2,4-Dihydroxyphenyl)nicotinonitrile hydrochloride

[0085] Bromo derivative used: 3-bromo-5-methylpyridine

[0086] Mass spectrum: MH⁺ 213 (100)

[0087] h. 1,3-Dihydroxy-4-(5-nitropyridin-2-yl)benzene hydrochloride

[0088] Bromo derivative used: 2-bromo-5-nitropyridine

[0089] Mass spectrum: MH⁺ 233 (100)

[0090] i. 1,3-Dihydroxy-4-(thiophen-3-yl)benzene

[0091] Bromo derivative used: 3-bromothiophene

[0092] Mass spectrum: MH⁺ 193 (100)

[0093] j. 4′-Methylbiphenyl-2,4-diol

[0094] Bromo derivative used: 4-bromotoluene

[0095] Mass spectrum: MH⁺ 201 (100)

[0096] k. Biphenyl-2,4,4′-triol

[0097] Bromo derivative used: 4-bromophenol

[0098] Mass spectrum: MH⁺ 203 (100)

[0099] l. Biphenyl-2,4,3′-triol

[0100] Bromo derivative used: 3-bromophenol

[0101] Mass spectrum: MH⁺ 203 (100)

[0102] m. 4′-Fluorobiphenyl-2,4-diol

[0103] Bromo derivative used: 4-bromofluorobenzene

[0104] Mass spectrum: MH⁺ 205 (100)

[0105] n. 1,3-Dihydroxy-4-(4-methylthiophen-3-yl)benzene

[0106] Bromo derivative used: 3-bromo-4-methylthiophene

[0107] Mass spectrum: MH⁺ 207 (100)

[0108] o. 2′,4′-Dihydroxybiphenyl-4-carbonitrile

[0109] Bromo derivative used: 4-bromobenzonitrile

[0110] Mass spectrum: MH⁺ 206 (100)

[0111] p. 1,3-Dihydroxy-4-(2-chlorothiophen-3-yl)benzene

[0112] Bromo derivative used: 3-bromo-2-chlorothiophene

[0113] Mass spectrum: MH⁺ 227 (100)

[0114] q. 1-(2′,4′-Dihydroxybiphenyl-3-yl)ethanone

[0115] Bromo derivative used: 5-bromoacetophenone

[0116] Mass spectrum: MH⁺ 229 (100)

[0117] r. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)benzene

[0118] Bromo derivative used: 5-bromo-1,3-methylenedioxybenzene

[0119] Mass spectrum: MH⁺ 231 (100)

[0120] s. 4′-Nitrobiphenyl-2,4-diol

[0121] Bromo derivative used: 4-bromonitrobenzene

[0122] Mass spectrum: MH⁺ 232 (100)

[0123] t. 2′-Nitrobiphenyl-2,4-diol

[0124] Bromo derivative used: 2-bromonitrobenzene

[0125] Mass spectrum: MH⁺ 232 (100)

[0126] u. 4′-Trifluoromethylbiphenyl-2,4-diol

[0127] Bromo derivative used: 4-bromotrifluorotoluene

[0128] Mass spectrum: MH⁺ 255 (100)

[0129] v. 2′,4′-Dimethylbiphenyl-2,4-diol

[0130] Bromo derivative used: 2-bromo-5-methyltoluene

[0131] Mass spectrum: MH⁺ 215 (100)

[0132] w. 3′-Methoxybiphenyl-2,4-diol

[0133] Bromo derivative used: 5-bromoanisole

[0134] Mass spectrum: MH⁺ 217 (100)

[0135] x. 4′-Chlorobiphenyl-2,4-diol

[0136] Bromo derivative used: 4-bromochlorobenzene

[0137] Mass spectrum: MH⁺ 221 (100)

[0138] y. 4′-Methylsulfanylbiphenyl-2,4-diol

[0139] Bromo derivative used: 4-methylsulfanylbromobenzene

[0140] Mass spectrum: MH⁺ 233 (100)

[0141] z. 1,3-Dihydroxy-4-(thiazol-2-yl)benzene

[0142] Bromo derivative used: 2-bromothiazole

[0143] Mass spectrum: MH⁺ 94 (100)

Example 2

[0144] Synthesis of 1,3-dihydroxybenzenes

[0145] The synthesis was accomplished by the method given in step C,Example 1.

[0146] a. 1,3-Dihydroxy-5-(pyridin-2-yl)benzene hydrochloride

[0147] Bromo derivative used: 3-bromopyridine

[0148] Mass spectrum: MH⁺ 188 (100)

[0149] b. 1,3-Dihydroxy-5-(pyrimidin-2-yl)benzene hydrochloride

[0150] Bromo derivative used: 2-bromopyrimidine

[0151] Mass spectrum: MH⁺ 189 (100)

[0152] c. 1,3-Dihydroxy-5-(thiophen-3-yl)benzene

[0153] Bromo derivative used: 3-bromothiophene

[0154] Mass spectrum: MH⁺ 193 (100)

[0155] d. 1,3-Dihydroxy-5-(thiophen-2-yl)benzene

[0156] Bromo derivative used: 2-bromothiophene

[0157] Mass spectrum: MH⁺ 192 (100)

[0158] e. 1,3-Dihydroxy-5-(thiazol-2-yl)benzene

[0159] Bromo derivative used: 2-bromothiazole

[0160] Mass spectrum: MH⁺ 94 (100)

[0161] f. 4′-Methylbiphenyl-2,4-diol

[0162] Bromo derivative used: 4-bromotoluene

[0163] Mass spectrum: MH⁺ 201 (100)

[0164] g. 1,3-Dihydroxy-4-(5-methylpyridin-2-yl)benzene hydrochloride

[0165] Bromo derivative used: 2-bromo-5-methylpyridine

[0166] Mass spectrum: MH⁺ 188 (100)

[0167] h. Biphenyl-3,5,4′-triol

[0168] Bromo derivative used: 4-bromophenol

[0169] Mass spectrum: MH⁺ 203 (100)

[0170] i. Biphenyl-3,5,3′-triol

[0171] Bromo derivative used: 3-bromophenol

[0172] Mass spectrum: MH⁺ 203 (100)

[0173] j. 4′-Fluorobiphenyl-3,5-diol

[0174] Bromo derivative used: 4-bromofluorobenzene

[0175] Mass spectrum: MH⁺ 205 (100)

[0176] k. 1,3-Dihydroxy-5-(3-methylthiophen-2-yl)benzene

[0177] Bromo derivative used: 2-bromo-3-methylthiophene

[0178] Mass spectrum: MH⁺ 206 (100)

[0179] l. 1,3-Dihydroxy-5-(4-methylthiophen-3-yl)benzene

[0180] Bromo derivative used: 3-bromo-4-methylthiophene

[0181] Mass spectrum: MH⁺ 207 (100)

[0182] m. 3′,5′-Dihydroxybiphenyl-4-carbonitrile

[0183] Bromo derivative used: 4-bromobenzonitrile

[0184] Mass spectrum: MH⁺ 206 (100)

[0185] n. 1,3-Dihydroxy-5-(2-chlorothiophen-3-yl)benzene

[0186] Bromo derivative used: 3-bromo-2-chlorothiophene

[0187] Mass spectrum: MH⁺ 227 (100)

[0188] o. 1-(2′,4′-Dihydroxybiphenyl-3-yl)ethanone

[0189] Bromo derivative used: 3-bromoacetophenone

[0190] Mass spectrum: MH⁺ 229 (100)

[0191] p. 1,3-Dihydroxy-4-(benzo[1,3]dioxol-5-yl)benzene

[0192] Bromo derivative used: 5-bromo-1,3-methylenedioxybenzene

[0193] Mass spectrum: MH⁺ 231 (100)

[0194] q. 4′-Nitrobiphenyl-2,4-diol

[0195] Bromo derivative used: 4-bromonitrobenzene

[0196] Mass spectrum: MH⁺ 232 (100)

[0197] r. 2′-Nitrobiphenyl-2,4-diol

[0198] Bromo derivative used: 2-bromonitrobenzene

[0199] Mass spectrum: MH⁺ 232 (100)

[0200] s. 1,3-Dihydroxy-5-(5-nitrothiophen-2-yl)benzene

[0201] Bromo derivative used: 2-bromo-5-nitrothiophene

[0202] Mass spectrum: MH⁺ 237 (100)

[0203] t. 4′-Trifluoromethylbiphenyl-3,5-diol

[0204] Bromo derivative used: 4-bromotrifluorotoluene

[0205] Mass spectrum: MH⁺ 255 (100)

[0206] u. 2′,4′-Dimethylbiphenyl-3,5-diol

[0207] Bromo derivative used: 2-bromo-5-methyltoluene

[0208] Mass spectrum: MH⁺ 215 (100)

[0209] v. 3′-Methoxybiphenyl-2,4-diol

[0210] Bromo derivative used: 5-bromoanisole

[0211] Mass spectrum: MH⁺ 217 (100)

[0212] w. 4′-Chlorobiphenyl-2,4-diol

[0213] Bromo derivative used: 4-bromochlorobenzene

[0214] Mass spectrum: MH⁺ 221 (100)

[0215] x. 4′-Methylsulfanylbiphenyl-2,4-diol

[0216] Bromo derivative used: 4-methylsulfanylbromobenzene

[0217] Mass spectrum: MH⁺ 233 (100)

[0218] y. 2′-Chloro-4′-nitrobiphenyl-3,5-diol

[0219] Bromo derivative used: 4-bromo-3-chloronitrobenzene

[0220] Mass spectrum: MH⁺ 266 (100)

Examples 3 to 53 Hair Colorants

[0221] Hair colorant solutions having the following composition wereprepared: 1.25 mmol of coupler of formula (I)/(Ia) as per Table 1 1.25mmol of developer as per Table 1 1.0 g of potassium oleate (8% aqueoussolution) 1.0 g of ammonia (22% aqueous solution) 1.0 g of ethanol 0.3 gof ascorbic acid to 100.0 g water

[0222] Just before use, 50 g of the foregoing coloring solution wasmixed with 50 g of a 6% aqueous hydrogen peroxide solution. The mixturewas then applied to bleached hair. After an exposure time of 30 min at40° C., the hair was rinsed with water, washed with a commercial shampooand dried. The resulting color shades are presented in Table 1. TABLE 1Coupler [sic - Translator] III. IV. II. 2,5- 4,5- Ex- I. 2,5- Diamino-Diamino-1- am- Coupler 1,4-Di- Diamino- phenyl- (2′-hydroxyeth- ple offormula amino- toluene ethanol yl)pyrazole No. (I)/(Ia) benzene sulfatesulfate sulfate 3 As per Ex. 1a dark dark dark purple brown brown brown4 As per Ex. 1b brown medium medium purple blond blond 5 As per Ex. 1cbrown medium medium purple blond blond 6 As per Ex. 1d medium brightbright bright blond blond blond purple 7 As per Ex. 1e medium brightbright bright blond blond blond purple 8 As per Ex. 1f medium brightbright bright blond blond blond purple 9 As per Ex. 1g medium brightbright bright blond blond blond purple 10 As per Ex. 1h medium brightbright bright blond blond blond purple 11 As per Ex. 1i medium blondblond bright blond purple 12 As per Ex. 1j medium bright bright brightblond blond blond purple 13 As per Ex. 1k medium bright bright brightblond blond blond purple 14 As per Ex. 1l brown bright bright purplepurple brown- brown- purple purple 15 As per Ex. 1m medium bright brightbright blond blond blond purple 16 As per Ex. 1n medium bright brightbright blond blond blond purple 17 As per Ex. 1o medium bright brightbright blond blond blond purple 18 As per Ex. 1p medium bright brightbright blond blond blond purple 19 As per Ex. 1q medium bright brightbright blond blond blond purple 20 As per Ex. 1r medium bright brightbright blond blond blond purple 21 As per Ex. 1s medium blond blondbright blond purple 22 As per Ex. 1t medium bright bright bright blondblond blond purple 23 As per Ex. 1u medium bright bright bright blondblond blond purple 24 As per Ex. 1v medium bright bright bright blondblond blond purple 25 As per Ex. 1w medium bright bright bright blondblond blond purple 26 As per Ex. 1x medium bright bright bright blondblond blond purple 27 As per Ex. 1y medium bright bright bright blondblond blond purple 28 As per Ex. 1z gray bright bright violet blue blue29 As per Ex. 2a blond bright bright bright blond blond orange 30 As perEx. 2b blond bright bright bright blond blond orange 31 As per Ex. 2cblond bright bright bright blond blond orange 32 As per Ex. 2d blondbright bright bright blond blond orange 33 As per Ex. 2e blond brightbright bright blond blond orange 34 As per Ex. 2f blond bright brightbright blond blond orange 35 As per Ex. 2g blond bright bright brightblond blond orange 36 As per Ex. 2h blond bright bright bright blondblond orange 37 As per Ex. 2i blond bright bright bright blond blondorange 38 As per Ex. 2j blond bright bright bright blond blond orange 39As per Ex. 2k blond bright bright bright blond blond orange 40 As perEx. 2l blond bright bright bright blond blond orange 41 As per Ex. 2mblond bright bright bright blond blond orange 42 As per Ex. 2n blondbright bright bright blond blond orange 43 As per Ex. 2o blond brightbright bright blond blond orange 44 As per Ex. 2p blond bright brightbright blond blond orange 45 As per Ex. 2q blond bright bright brightblond blond orange 46 As per Ex. 2r blond bright bright bright blondblond orange 47 As per Ex. 2s blond bright bright bright blond blondorange 48 As per Ex. 2t blond bright bright bright blond blond orange 49As per Ex. 2u blond bright bright bright blond blond orange 50 As perEx. 2v blond bright bright bright blond blond orange 51 As per Ex. 2wblond bright bright bright blond blond orange 52 As per Ex. 2x blondbright bright bright blond blond orange 53 As per Ex. 2y blond brightbright bright blond blond orange

Examples 54 to 63 Hair Colorants

[0223] Hair colorant solutions of the following composition wereprepared: X g of 1,3-dihydroxy-5-(thiophenyl-2-yl)benzene (coupler K1)[sic - Tr.] U g of developer E8 to E15 as per Table 2 Y g of coupler K11to K33 as per Table 3 Z g of direct dye D2 or D3 as per Table 4 10.0 gof potassium oleate (8% aqueous solution) 10.0 g of ammonia (22% aqueoussolution) 10.0 g of ethanol 0.3 g of ascorbic acid to 100.0 g water

[0224] Just before use, 30 g of the foregoing coloring solution wasmixed with 30 g of a 6% aqueous solution of hydrogen peroxide. Themixture was then applied to bleached hair. After an exposure time of 30min at 40° C., the hair was rinsed with water, washed with a commercialshampoo and dried. Table 5 shows the coloring results. TABLE 2Developers E8 1,4-diaminobenzene E9 2,5-diaminophenylethanol sulfate E103-methyl-4-aminophenyl E11 4-amino-2-aminomethylphenol dihydrochlorideE12 4-aminophenol E13 N,N-bis(2′-hydroxyethyl)-p-phenylenediaminesulfate E14 4,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate E152,5-diaminotoluene sulfate

[0225] TABLE 3 Couplers K1 1,3-dihydroxy-5-(thiophenyl-2-yl)benzene[sic - Translator] K2 1,3-dihydroxy-4-(thiophenyl-2-yl)benzene [sic -Translator] K12 2-amino-4-(2′-hydroxyethyl)aminoanisole sulfate K131,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K18N-(3-dimethylamino)phenylurea K19 1,3-bis(2,4-diaminophenoxy)propanetetrahydrochloride K21 3-aminophenol K22 5-amino-2-methylphenol K233-amino-2-chloro-6-methylphenol K24 5-amino-4-fluoro-2-methylphenolsulfate K25 1-naphthol K26 1-acetoxy-2-methylnaphthalene K311,3-dihydroxybenzene K32 2-methyl-1,3-dihydroxybenzene K331-chloro-2,4-dihydroxybenzene

[0226] TABLE 4 Direct Dyes D2 6-chloro-2-ethylamino-4-nitrophenol D32-amino-6-chloro-4-nitrophenol

[0227] TABLE 5 Hair Colorants Example No. 54 55 56 57 58 59 Dyes(Quantity of dye in grams) K1 0.10 0.10 0.13 0.15 0.20 0.10 E8 0.30 E90.25 0.30 E15 0.25 0.30 0.25 K12 0.16 K12 0.16 [sic - Transl.] K13 0.050.15 0.15 K18 0.10 K19 0.15 K13 [sic] 0.05 0.10 0.15 0.15 0.15 K31 0.05K32 0.05 K33 0.10 K21 0.05 K22 0.05 K23 0.05 0.10 0.10 0.10 Dyeing blondblond blond blond blond blond result Example No. 60 61 62 63 Dyes(Quantity of dye in grams) K1 0.20 0.20 0.20 0.20 E8 0.15 0.20 E15 0.200.18 E10 0.30 E11 0.30 E12 0.30 E14 0.30 K25 0.30 0.30 0.30 K26 0.35Dyeing red-brown red-brown red-brown red-brown result

Examples 64 to 69 Hair Colorants

[0228] Dye carriers in cream form and having the following compositionwere prepared: X g of 1,3-dihydroxy-5-(thiophenyl-2-yl)benzene (couplerK1) [sic - Tr.] U g of developer E8 \to E15 as per Table 2 Y g ofcoupler K11 to K33 as per Table 3 Z g of direct dye D2 or D3 as perTable 4 15.0 g of cetyl alcohol 0.3 g of ascorbic acid 3.5 g of sodiumlauryl alcohol diethylene glycol ether sulfate, 28% aqueous solution 3.0g of ammonia, 22% aqueous solution 0.3 g of sodium sulfite, anhydrous to100.0 g water

[0229] Just before use, 30 g of the foregoing coloring cream was mixedwith 30 g of a 6% solution of hydrogen peroxide. The mixture was thenapplied to the hair. After an exposure time of 30 min at 40° C., thehair was rinsed with water, washed with a commercial shampoo and dried.The coloring results are presented in Table 6. TABLE 6 Hair ColorantsExample No. 64 65 66 67 68 69 Dyes (Quantity of dye in grams) K1 1.101.10 0.60 0.20 0.40 0.40 E8 1.50 E13 1.60 0.70 E15 1.80 0.70 0.70 K120.60 K13 0.70 1.50 1.25 0.18 0.18 0.18 K23 0.05 0.10 0.10 0.10 K31 0.600.20 D3 0.10 D2 0.10 0.10 Dyeing black black black brown brown brownresult

Examples 70 to 79 Hair Colorants

[0230] Hair colorant solutions of the following composition wereprepared: X g of 1,3-dihydroxy-4-(thiophen-2-yl)benzene (coupler K2) U gof developer E8 \to E15 as per Table 2 Y g of coupler K11 to K33 as perTable 3 10.0 g of potassium oleate (8% aqueous solution) 10.0 g ofammonia (22% aqueous solution) 10.0 g of ethanol 0.3 g of ascorbic acidto 100.0 g water

[0231] Just before use, 30 g of the foregoing coloring solution wasmixed with 30 g of a 6% aqueous solution of hydrogen peroxide. Themixture was then applied to bleached hair. After an exposure time of 30min at 40° C., the hair was rinsed with water, washed with a commercialshampoo and dried. Table 7 shows the coloring results. TABLE 7 HairColorants Example No. 70 71 72 73 74 75 Dyes (Quantity of dye in grams)K2 0.10 0.10 0.13 0.15 0.20 0.10 E8 0.30 E9 0.25 0.30 E15 0.25 0.30 0.25K12 0.16 K13 0.05 0.15 0.15 K18 0.10 K19 0.15 K21 0.05 K22 0.05 K23 0.050.10 0.10 K24 0.10 K31 0.05 K32 0.05 K33 0.10 Dyeing blond blond blondblond blond blond result Example No. 76 77 78 79 Dyes (Quantity of dyein grams) K1 0.20 0.20 0.20 0.20 [sic - Tr.] E8 0.15 0.20 E10 0.30 E110.30 E12 0.30 E14 0.30 E15 0.20 0.18 K25 0.30 0.30 0.30 K26 0.35 Dyeingred-brown red-brown red-brown red-brown result

Examples 80 to 86 Hair Colorants

[0232] Dye carriers in cream form and having the following compositionwere prepared: X g of 1,3-dihydroxy-4-(thiophen-2-yl)benzene (couplerK2) U g of developer E8 to E15 as per Table 2 Y g of coupler K11 to K33as per Table 3 Z g of direct dye D2 or D3 as per Table 4 15.0 g of cetylalcohol 0.3 g of ascorbic acid 3.5 g of sodium lauryl alcohol diethyleneglycol ether sulfate, 28% aqueous solution 3.0 g of ammonia, 22% aqueoussolution 0.3 g of sodium sulfite, anhydrous to 100 g water

[0233] Just before use, 30 g of the foregoing coloring cream was mixedwith 30 g of a 6% solution of hydrogen peroxide. The mixture was thenapplied to the hair. After an exposure time of 30 min at 40° C., thehair was rinsed with water, washed with a commercial shampoo and dried.The coloring results are presented in Table 8. TABLE 8 Hair ColorantsExample No. 80 81 83 84 85 86 Dyes (Quantity of dye in grams) K1 [sic]1.10 1.10 0.6 0.20 0.40 0.40 E8 1.50 E13 1.60 0.70 E15 1.80 0.70 0.70K12 0.60 K13 0.70 1.50 1.25 0.18 0.18 0.18 K23 0.05 0.10 0.10 0.10 K310.60 0.20 D3 0.10 D2 0.10 0.10 Dyeing black black black brown brownbrown result

[0234] Unless otherwise indicated, all percentages given in the presentpatent application are by weight.

1. 1,3-Dihydroxy-4-heteroarylbenzene derivatives of general formula (I)or the physiologically tolerated, water-soluble salts thereof

wherein X denotes oxygen, sulfur or N—R5; R1 and R2 can be equal ordifferent and independently of each other denote hydrogen, a halogenatom, a hydroxyl group, a C₁-C₄-alkoxy group, a C₁-C₄-hydroxyalkoxygroup, a C₁-C₆-alkyl group, a C₁-C₄-alkylthioether group, atrifluoromethyl group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl group ora C₂-C₄-dihydroxyalkyl group; R3 and R4 can be equal or different andindependently of each other denote hydrogen, a hydroxyl group, a halogenatom, a cyano group, a C₁-C₄-alkoxy group, a C₁-C₆-alkyl group, aC₁-C₄-alkylthioether group, a mercapto group, a nitro group, an aminogroup, a C₁-C₄-alkylamino group a di(C₁-C₄)alkylamino group, a —C(O)Hgroup, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃ group, aC₁-C₄-hydroxyalkyl group or a C₂-C₄-dihydroxyalkyl group; and R5 denoteshydrogen, a C₁-C₆-alkyl group, a C₂-C₄-hydroxyalkyl group, a phenylgroup or an acetyl group.
 2. 1,3-Dihydroxy-4-heteroarylbenzenederivative according to claim 1, characterized in that it is selectedfrom among compounds of formula (I) wherein (i) one or more of the R1,R2, R3 and R4 groups denote hydrogen and X denotes sulfur or oxygen or(ii) R1 and R2 simultaneously denote hydrogen and X denotes sulfur. 3.1,3-Dihydroxy-4-heteroarylbenzene derivative of formula (I) according toclaim 1 or 2, characterized in that it is selected from the groupconsisting of 1,3-dihydroxy-4-(thiophen-2-yl)benzene,1,3-dihydroxy-4-(5-nitrothiophen-2-yl)benzene,1,3-dihydroxy-4-(3-methylthiophen-2-yl)benzene and1,3-dihydroxy-4-(furan-2-yl)benzene and the physiologically toleratedsalts thereof.
 4. 1,3-Dihydroxybenzene derivative of formula (Ia) or aphysiologically tolerated, water-soluble salt thereof

wherein R′1 denotes a substituted pyridyl group, a pyrimidyl group, agroup of formula

or a group of formula

wherein R′2, R′3, R′4, R′5 and R′6 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxylgroup, a C₁-C₄-alkoxy group, a C₁-C₄-hydroxyalkoxy group, a C₁-C₆-alkylgroup, a C₁-C₄-alkylthioether group, a mercapto group, a nitro group, anamino group, a C₁-C₄-alkylamino group, a hydroxy(C₁-C₄)alkylamino group,a di(C₁-C₄)alkylamino group, a di[hydroxy(C₁-C₄)-alkyl]amino group, adihydroxy-(C₃-C₄)-alkylamino group, a[hydroxy-(C₁-C₄)-alkyl]-C₁-C₄-alkylamino group, a trifluoromethyl group,a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃ group,a C₁-C₄-hydroxyalkyl group or a C₂-C₄-dihydroxyalkyl group, or twoadjacent R2 to R6 groups form an —O—CH₂—O— bridge; X′1 denotes sulfur,nitrogen, oxygen, C—R′9 or N—R′8; X′2 denotes sulfur, nitrogen, oxygen,C—R′10 or N—R′8; X′3 denotes sulfur, nitrogen, oxygen, C—R′11 or N—R′8;R′7, R′9, R′10 and R′11 independently of each other denote hydrogen, ahalogen atom (F, Cl, Br, I), a cyano group, a C₁-C₄-alkoxy group, aC₁-C₆-alkyl group, a C₁-C₄-alkylthioether group, a mercapto group, anitro group, an amino group, a C₁-C₄-alkylamino group, adi(C₁-C₄)-alkylamino group, a di(C₁-C₄-hydroxyalkyl)amino group, aC₁-C₄-hydroxyalkylamino group, a trifluoromethyl group, a —C(O)CH₃group, a —C(O)CF₃ group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl groupor a C₃-C₄-dihydroxyalkyl group; and R′8 denotes hydrogen, a C₁-C₆-alkylgroup, a C₂-C₄-hydroxyalkyl group, a phenyl group or an acetyl group,provided that at least one and at the most two of the X′1 to X′3 groupsdenote C—R′9, C—R′10 or C—R′11 and at the most one of the X′1 to X′3groups denotes sulfur, oxygen or N—R′8, and R′1 does not stand for aphenyl group or hydroxyphenyl group.
 5. Agent for oxidative dyeing ofkeratin fibers based on a developer-coupler combination, characterizedin that it contains at least one 1,3-dihydroxy-4-heteroarylbenzenederivative of formula (I) according to one of claims 1 to
 3. 6. Agentfor dyeing keratin fibers based on a developer-coupler combination,characterized in that it contains at least one 1,3-dihydroxybenzenederivative of formula (Ia) or a physiologically tolerated, water-solublesalt thereof

wherein R′1 denotes a substituted pyridyl group, a pyrimidyl group, agroup of formula

or a group of formula

wherein R′2, R′3, R′4, R′5 and R′6 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxylgroup, a C₁-C₄-alkoxy group, a C₁-C₄-hydroxyalkoxy group, a C₁-C₆-alkylgroup, a C₁-C₄-alkylthioether group, a mercapto group, a nitro group, anamino group, a C₁-C₄-alkylamino group, a hydroxy(C₁-C₄)alkyl aminogroup, a di(C₁-C₄)alkylamino group, a di[hydroxy-(C₁-C₄)-alkyl]aminogroup, a dihydroxy-(C₃-C₄)-alkylamino group, a[hydroxy-(C₁-C₄)-alkyl]-C₁-C₄-alkylamino group, a trifluoromethyl group,a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, an —Si(CH₃)₃ group,a C₁-C₄-hydroxyalkyl group or a C₂-C₄-dihydroxyalkyl group, or twoadjacent R2 to R6 groups form an —O—CH₂—O— bridge; X′1 denotes sulfur,nitrogen, oxygen, C—R′9 or N—R′8; X′2 denotes sulfur, nitrogen, oxygen,C—R′10 or N—R′8; X′3 denotes sulfur, nitrogen, oxygen, C—R′11 or N—R′8;R′7, R′9, R′10 and R′11 independently of each other denote hydrogen, ahalogen atom (F, Cl, Br, I), a cyano group, a C₁-C₄-alkoxy group, aC₁-C₆-alkyl group, a C₁-C₄-alkylthioether group, a mercapto group, anitro group, an amino group, a C₁-C₄-alkylamino group, adi(C₁-C₄)-alkylamino group, a di(C₁-C₄-hydroxyalkyl)amino group, aC₁-C₄-hydroxyalkylamino group, a trifluoromethyl group, a —C(O)CH₃group, a —C(O)CF₃ group, an —Si(CH₃)₃ group, a C₁-C₄-hydroxyalkyl groupor a C₃-C₄-dihydroxyalkyl group; and R′8 denotes hydrogen, a C₁-C₆-alkylgroup, a C₂-C₄-hydroxyalkyl group, a phenyl group or an acetyl group,provided that at least one and at the most two of the X′1 to X′3 groupsdenote C—R′9, C—R′10 or C—R′11 and at the most one of the X′1 to X′3groups denotes sulfur, oxygen or N—R′8.
 7. Agent according to claim 6,characterized in that it is selected from among compounds of formula(Ia) wherein (i) X′2 denotes C—R′10 and X′1 denotes sulfur and X′3denotes C—R′11 or X′1 denotes C—R′9 and X′3 denotes sulfur or (ii) X′2denotes C—R′10 and X′1 denotes sulfur and X′3 denotes C—R′11 or X′1denotes C—R′9 and X′3 denotes sulfur and at least one of the R′9 to R′11groups denotes hydrogen.
 8. Agent according to one of claims 5 to 7,characterized in that the compound of formula (I) and (Ia) is selectedfrom the group consisting of 1,3-dihydroxy-4-(thiophen-2-yl)benzene,1,3-dihydroxy-4-(5-nitrothiophen-2-yl)benzene,1,3-dihydroxy-4-(3-methylthiophen-2-yl)benzene,1,3-dihydroxy-4-(furan-2-yl)benzene,1,3-dihydroxy-5-(5-chlorothiophen-2-yl)benzene,1,3-dihydroxy-5-(3-methylthiophen-2-yl)benzene,1,3-dihydroxy-4-(thiophen-3-yl)benzene and1,3-dihydroxy-5-(thiophen-3-yl)benzene and the physiologically toleratedsalts thereof.
 9. Agent according to one of claims 5 to 8, characterizedin that it contains the 1,3-dihydroxy-4-heteroarylbenzene of formula (I)and/or the 1,3-dihydroxybenzene of formula (Ia) in an amount from 0.005to 20 wt. %.
 10. Agent according to one of claims 5 to 9, characterizedin that the developer is selected from the group consisting of1,4-diaminobenzene; 1,4-diamino-2-methylbenzene;1,4-diamino-2,6-dimethylbenzene; 1,4-diamino-3,5-diethylbenzene;1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diaminobenzene; 1,4-diamino-2-(thiophen-2-yl)benzene;1,4-diamino-2-(thiophen-3-yl)benzene;1,4-diamino-2-(pyridin-3-yl)benzene; 2,5-diaminobiphenyl;1,4-diamino-2-methoxymethylbenzene; 1,4-diamino-2-aminomethylbenzene;1,4-diamino-2-hydroxymethylbenzene;1,4-diamino-2-(2-hydroxyethoxy)benzene;2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene; 4-phenylaminoaniline;4-dimethylaminoaniline; 4-diethylaminoaniline; 4-dipropylaminoaniline;4-[ethyl-(2-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]aniline;4-[di(2-hydroxyethyl)amino]-2-methylaniline;4-[(2-methoxyethyl)amino]aniline; 4-[(3-hydroxypropyl)amino]aniline;4-[(2,3-dihydroxypropyl)amino]aniline;1,4-diamino-2-(1-hydroxyethyl)benzene;1,4-diamino-2-(2-hydroxyethyl)benzene;1,4-diamino-2-(1-methylethyl)benzene;1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol;1,4-bis-[(4-aminophenyl)amino]butane;1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol;4-amino-3-fluorophenol; 4-methylaminophenol;4-amino-2-(aminomethyl)phenol; 4-amino-2-(hydroxymethyl)phenol;4-amino-2-fluorophenol; 4-amino-2-[(2-hydroxyethyl)amino]-methylphenol;4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol;4-amino-2-(2-hydroxyethyl)phenol; 5-aminosalicylic acid;2,5-diaminopyridine; 2,4,5,6-tetraamino-pyrimidine;2,5,6-triamino-4-(1H)-pyrimidone;4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-(1-methylethyl)-1H-pyrazole;4,5-diamino-1-[(4-methylphenyl)-methyl]-1H-pyrazole;1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole;4,5-diamino-1-methyl-1H-pyrazole; 2-aminophenol; 2-amino-6-methylphenol;2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.
 11. Agent accordingto one of claims 5 to 10, characterized in that in addition to thecompounds of formula (I) and/or (Ia) it contains other known couplersfrom the group consisting of N-(3-dimethylaminophenyl)urea;2,6-diaminopyridine; 2-amino-4-[(2-hydroxyethyl)amino]anisole;2,4-diamino-1-fluoro-5-methylbenzene;2,4-diamino-1-methoxy-5-methylbenzene;2,4-diamino-1-ethoxy-5-methylbenzene;2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene;2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene;2,3-diamino-6-methoxypyridine;3-amino-6-methoxy-2-(methylamino)pyridine;2,6-diamino-3,5-dimethoxypyridine; 3,5-diamino-2,6-dimethoxypyridine;1,3-diaminobenzene; 2,4-diamino-1-(2-hydroxyethoxy)benzene;1,3-diamino-4-(2,3-dihydroxypropoxy)benzene;1,3-diamino-4-(3-hydroxypropoxy)benzene;1,3-diamino-4-(2-methoxyethoxy)benzene;2,4-diamino-1,5-di(2-hydroxyethoxy)benzene;1-(2-aminoethoxy)-2,4-diaminobenzene;2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene;2,4-diaminophenoxyacetic acid; 3-[di(2-hydroxyethyl)amino]aniline;4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene;5-methyl-2-(1-methylethyl)phenol; 3-[(2-hydroxyethyl)amino]aniline;3-[(2-aminoethyl)amino]aniline; 1,3-di(2,4-diaminophenoxy)propane;di(2,4-diaminophenoxy)methane; 1,3-diamino-2,4-dimethoxybenzene;2,6-bis(2-hydroxyethyl)aminotoluene; 4-hydroxyindole;3-dimethylaminophenol; 3-diethylaminophenol; 5-amino-2-methylphenol;5-amino-4-fluoro-2-methylphenol; 5-amino-4-methoxy-2-methylphenol;5-amino-4-ethoxy-2-methylphenol; 3-amino-2,4-dichlorophenol;5-amino-2,4-dichlorophenol; 3-amino-2-methylphenol;3-amino-2-chloro-6-methylphenol; 3-aminophenol;2-[(3-hydroxyphenyl)amino]acetamide;5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol;5-[(2-hydroxyethyl)amino]-2-methylphenol;3-[(2-hydroxyethyl)amino]phenol; 3-[(2-methoxyethyl)amino]phenol;5-amino-2-ethylphenol; 5-amino-2-methoxyphenol;2-(4-amino-2-hydroxyphenoxy)ethanol;5-[(3-hydroxypropyl)amino]-2-methylphenol;3-[(2,3-dihydroxypropyl)amino]-2-methylphenol;3-[(2-hydroxyethyl)amino]-2-methylphenol; 2-amino-3-hydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 5-amino-4-chloro-2-methylphenol;1-naphthol; 2-methyl-1-naphthol; 1,5-dihydroxynaphthalene;1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene;2,7-dihydroxynaphthalene; 2-methyl-1-naphthol acetate;1,3-dihydroxybenzene; 1-chloro-2,4-dihydroxybenzene;2-chloro-1,3-dihydroxybenzene;1,2-dichloro-3,5-dihydroxy-4-methylbenzene;1,5-dichloro-2,4-dihydroxybenzene; 1,3-dihydroxy-2-methylbenzene;3,4-methylenedioxyphenol; 3,4-methylenedioxyaniline;5-[(2-hydroxyethyl)amino]-1,3-benzodioxole;6-bromo-1-hydroxy-3,4-methylenedioxybenzene; 3,4-diaminobenzoic acid;3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine;6-amino-3,4-dihydro-1,4[2H]benzoxazine; 3-methyl-1-phenyl-5-pyrazolone;5,6-dihydroxyindole; 5,6-dihydroxyindoline; 5-hydroxyindole;6-hydroxyindole; 7-hydroxyindole and 2,3-indolinedione.
 12. Agentaccording to one of claims 5 to 11, characterized in that it containseach of the developers and couplers in a total amount of 0.005 to 20 wt.%, based on the total amount of the dyeing agent.
 13. Agent according toone of claims 5 to 12, characterized in that additionally it contains atleast one direct dye.
 14. Agent according to one of claims 5 to 13,characterized in that it has a pH of 6.5 to 11.5.
 15. Agent according toone of claims 5 to 14, characterized in that it is a hair colorant.